Cooperativity in a spin transition ferrous polymer: Interacting domain model, thermodynamic, optical and EPR study

Abstract:

A new thermodynamic model is proposed in order to account for the high spin low spin conversion in metal-organic polymers. The model, based on the idea that the spin conversion occurs in interacting domains of like-spin metal ions, allows to explain most of the important features of various types of spin conversion. The sine qua non condition of the existence of spin transitions with hysteresis is obtained. In the case of very large cooperativity, the model predicts unusual behaviour of the spin conversion system due to a low-temperature metastable high spin state. Existence of such a state is interesting in the context of the light induced excited spin state trapping recently observed in some ferrous compounds. The model is applied to interpret the spin transition in polycrystalline ferrous polymer [Fe _1-y Cu _y (Htrz)₂ trz] (BF ₄) with y = 0.00, 0.01 and 0.10, detected by differential scanning calorimetry, optical reflectivity and electron paramagnetic resonance. The domain size and the interaction energy between the domains are estimated as, respectively, n = 11 and for the y = 0 compound. As the copper content is growing, n and tend to decrease, resulting in transformations of the shape of hysteresis loop which becomes less steep, narrows and shifts to lower temperatures. The electron paramagnetic resonance gives further evidence of the presence of like-spin domains.